The authors have performed angle-resolved x-ray photoelectron diffraction (XPD) from a Si(100)-c(4x2) surface to study the structural origin of Si-2p core-level shifts. In the experiment, the highly resolved surface Si-2p core-level spectra were measured as a fine grid of hemisphere and photon energies, using the SpectroMicroscopy Facility {open_quotes}ultraESCA{close_quotes} instrument. By carefully decomposing the spectra into several surface peaks, the authors are able to obtain surface-atom resolved XPD patterns. Using a multiple scattering analysis, they derived a detailed atomic model for the Si(100)-c(4x2) surface. In this model, the asymmetric dimers were found tilted by 11.5 plus/minus 2.0 degrees with bond length of 2.32 plus/minus 0.05{angstrom}. By matching model XPD patterns to experiment, the authors can identify which atoms in the reconstructed surface are responsible for specific photoemission lines in the 2p spectrum.